EP0100444A2 - Use of binders based on carboxyl-containing copolymers in aqueous printing inks - Google Patents

Use of binders based on carboxyl-containing copolymers in aqueous printing inks Download PDF

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Publication number
EP0100444A2
EP0100444A2 EP83106412A EP83106412A EP0100444A2 EP 0100444 A2 EP0100444 A2 EP 0100444A2 EP 83106412 A EP83106412 A EP 83106412A EP 83106412 A EP83106412 A EP 83106412A EP 0100444 A2 EP0100444 A2 EP 0100444A2
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weight
molecular weight
printing
polymerization
printing inks
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German (de)
French (fr)
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EP0100444B1 (en
EP0100444A3 (en
EP0100444B2 (en
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Juergen Dr. Hambrecht
Volker Dr. Muench
Heinz-Hilmar Bankowsky
Eckehardt Dr. Wistuba
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BASF SE
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BASF SE
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/106—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C09D11/107—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds from unsaturated acids or derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring

Definitions

  • the invention relates to a method. for the production of printing ink binders by polymerizing a monomer mixture of vinyl aromatics and monoolefinically unsaturated carboxylic acids and their use as binders for aqueous printing inks for printing on paper, plastic and metal foils.
  • Aqueous printing inks are mainly used for printing on paper and corrugated cardboard. Increased requirements for air pollution control have led to an increasing demand for aqueous printing inks, even for non-absorbent printing media.
  • the object of the invention was therefore to provide a process for the production of printing ink binders with which binders are obtained which do not have the above disadvantages.
  • these binders should be soluble and water-dilutable in the weakly alkaline range.
  • the binder solution should have a low viscosity even with only a small proportion of water-miscible organic solvents.
  • the printing inks produced with the binder should also have good pigment compatibility, viscosity stability after storage, neutral odor and good printability.
  • the wet wipe resistance after drying of the printing ink and the adhesive strength on the substrate are also of significant importance. Furthermore, absolute batch constancy of the aqueous printing inks should be ensured
  • the continuous bulk polymerization of the monomer mixture is preferably carried out with residence times of ⁇ 30 minutes.
  • the present invention also relates to the use of the copolymers containing carboxyl groups prepared according to the invention as binders for aqueous printing inks for printing on paper, plastic and metal foils.
  • Resins are known from DE-OS 25 02 172, which among other things. by thermal copolymerization - that is to say without free-radical initiators - from 2 to 25% by weight of acrylic acid, styrene and maleic anhydride at about 150 to 300 ° C. These resins are poorly or not at all alkali-soluble and are recommended as paper sizes according to the publication mentioned. However, they are not suitable as a resin component for the binder solution of aqueous printing inks, since they have insufficient water solubility and adhesive strength on non-absorbent print media.
  • the acidic resins according to the invention do not have these disadvantages. It is surprising that with regard to the discontinuously produced resin of DE-AS 15 19 201 by continuous, purely thermal bulk polymerization at temperatures from 200 ° to 400 ° C. and low residence times, products with a structure that is similar per se, but for use As a binder in aqueous printing inks, substantially improved properties, in particular with regard to the adhesive strength on non-absorbent printing media, the wet smear resistance and the storage stability, can be obtained.
  • the new binder resins lead to glossy prints with a flawless surface when processing the aqueous printing inks produced therewith.
  • Nitriles e.g. Acrylonitrile or methacrylonitrile, amides, such as acrylamide or maleic acid or fumaric acid dialkyl esters of alcohols containing 1 to 8 carbon atoms.
  • Preferred monomers (C) are e.g. n-butyl acrylate, methyl methacrylate and / or acrylonitrile.
  • These monomers (C) can be present in the monomer mixture up to 10, preferably 2 to 7 percent by weight, based on the total amount of monomers (A) + (B) + (C), or copolymerized in the copolymer.
  • Copolymers which contain acrylic acid and / or methacrylic acid as component (A) and styrene and / or vinyltoluene as component (B) are preferred, component (A) also being able to contain maleic acid or fumaric acid units.
  • the copolymerization is carried out continuously at temperatures between 200 and 400, preferably between 220 and 380 ° C. and in the absence of free radical initiators and regulators.
  • a copolymer of styrene and acrylic acid can be prepared, for example, by continuously feeding the monomers to a reactor or two series-connected polymerization zones, for example a pressure vessel cascade, and after a residence time of 3 to 30, preferably 5 to 25, minutes at temperatures between 200 and 400 ° C continuously discharged from the reaction zone. It is important to keep to these temperature limits, as the dwell times are too long and the molecular weights too high if the temperature is too low, and thermal decomposition processes can occur if they are exceeded.
  • a polymerization vessel, a pressure vessel cascade, a pressure tube or a pressure boilers with a downstream reaction tube equipped with a static mixer can be used.
  • the monomer mixture (A) + (B) + optionally (C) is preferably polymerized in at least two polymerization zones connected in series.
  • One reaction zone can consist of a pressure-tight vessel, the other of a pressure-tight reaction tube, preferably a heatable static mixer. If the polymerization is carried out in two zones connected in series, conversions are obtained which are above 99%.
  • thorough mixing of the components must be ensured, for example using pressure-tight vessels which are equipped with a stirrer, or polymerization tubes with static mixers.
  • the polymerization can be carried out at pressures of> 1 bar, preferably between 1 and 200 bar. Particularly good results are obtained if the polymerization reaction is carried out with periodic pressure fluctuations with pressure differences between 5 and 120 bar and then also relaxed with periodic pressure fluctuations with the same pressure differences. This measure, which results in a pulsating flow of the reaction material, causes the reactor to self-clean and prevents product-damaging wall coverings and caking in the reactor.
  • the product discharge is homogeneous and contains no specks or cracked material.
  • Continuous polymerization for the purposes of the present invention should also be understood to mean a procedure in which about 10% of the monomer mixture is initially introduced in a polymerization zone, for example in a kettle, and in which the rest of the monomer mixture is then subsequently introduced continuously Course of 10 up to 30 minutes.
  • the space-time yields are not as high as in the case of continuous polymerization in two reaction zones connected in series.
  • polymerization is preferably carried out in the absence of a solvent. With appropriate selection of the monomer composition and the amount of monomers used per unit of time, the amount of heat released during the polymerization is sufficient to maintain the temperature required for the polymerization. Occasionally, however, it may be necessary to heat or cool the reaction zone.
  • the copolymers prepared by the process according to the invention therefore only contain such small amounts of unconverted monomers that it is generally not necessary to remove the remaining small amounts of monomers from the polymer.
  • the polymer can be degassed in vacuo.
  • Known evaporation units such as tube evaporators, plate evaporators or film extruders are used for this purpose.
  • a degassing step is not necessary for the production of the polymers according to the invention.
  • the molecular weight of the copolymers prepared according to the invention is 400 to 4000, preferably 500 to 2000. It can be controlled on the one hand via the polymerization temperature and on the other hand via the residence time.
  • the copolymer can be continuously extracted from the polymerization apparatus e.g. are discharged via a relaxation vessel with a downstream discharge unit or preferably in a pulsating manner.
  • a relaxation vessel with a downstream discharge unit or preferably in a pulsating manner.
  • the carboxyl groups of the copolymer are therefore partially or up to 100% neutralized in these cases following the polymerization with bases.
  • Suitable bases are, for example, gaseous ammonia, aqueous ammonia solutions or aqueous solutions of other bases such as sodium hydroxide solution, potassium hydroxide solution, alkaline earth metal hydroxides such as magnesium hydroxide and calcium hydroxide or amines such as monoalkylamines, dialkylamines and trialkylamines or mixtures of the amines and alkanolamines such as e.g. Dimethylethanolamine.
  • Neutralization is generally carried out in such a way that copolymer solutions are obtained which have a solids content of between 10 and 40% by weight.
  • the aqueous, partially or completely neutralized copolymer solutions can easily be diluted by adding water.
  • the aqueous solution can also contain up to 10% by weight of an alkanol having 1 to 4 carbon atoms.
  • alkanols are methanol, ethanol, isopropanol and n-butanol; Isopropanol is preferably used.
  • the binder resins can also be dissolved continuously immediately after the copolymerization.
  • the hot polymer melt coming from the reactor is then dissolved at temperatures of 80 to 200 ° C., pressures above 1 bar and residence times of 5 to 30 minutes.
  • solution apparatus can eg pressure vessels, pressure pipes, which may contain built-in mixing elements, or combinations of pressure vessels and pressure pipes may also be used. Combinations of pressure pipes are preferably used which are at least partially equipped with mixing elements. These organs can be rods or sieve plates.
  • Mixing elements are preferably used which break the reaction mass into different streams with the lowest possible flow resistance and bring them together again by changing the flow direction.
  • mixing elements are static mixers.
  • the content of the reactor system is generally such that, given the residence time of 5 to 30 minutes, high space-time yields, e.g. can be achieved in the range of 1 to 50 kg copolymer per liter and hour.
  • the partially neutralized or completely neutralized copolymer is discharged from the polymerization device with pulsating relaxation.
  • the pressure during the dissolving process is more than 1 bar and is preferably in the range from 5 to 120 bar.
  • the aqueous printing inks generally contain a binder solution which is composed of
  • Solutions of this concentration and composition have a flow time of 10 - 30 seconds in the flow cup according to DIN 53 211.
  • the binders produced by the process according to the invention result in printing inks of constant quality, with regard to storage stability, gloss, adhesive strength, behavior on the printing press and in particular wet wiping resistance and odor neutrality.
  • they are also suitable for aqueous gravure printing.
  • the pigments used to make the inks can be selected from the usual pigments that are useful for gravure or flexographic inks.
  • the printing ink can additionally microcrystalline wax, polyethylene wax may. as an aqueous dispersion, or other modifiers customary for printing inks can be added.
  • the binder solutions are generally added to the aqueous printing inks at -40-90% by weight, preferably 45-80% by weight.
  • Mixing with pigment preparations or rubbing with inorganic and organic pigments can be carried out with the usual mixing or rubbing aggregates. It is particularly advantageous; when using pigments which have been equipped in a special finishing process for dispersion in aqueous media or aqueous pigment preparations.
  • Example 1 70 parts of styrene and 30 parts of acrylic acid were copolymerized in accordance with Example 1.
  • the temperature was 290 ° C., the residence time 15 minutes and the pressure between 5 and 60 bar.
  • Example 1 60 parts of styrene, 34 parts of acrylic acid and 6 parts of methyl acrylate were copolymerized in accordance with Example 1.
  • the temperature was 300 ° C, the pressure 10 to 80 bar and the residence time 9 minutes.
  • Example 1 60 parts of styrene, 35 parts of acrylic acid and 5 parts of maleic anhydride were polymerized according to Example 1. The temperature was 280 ° C, the pressure was 20-60 bar, the residence time was 10 minutes.
  • the binder resin X 4 obtained had an average molecular weight of M n of 1070 and had a molecular weight non-uniformity of 2.0.
  • Example 1 of GB-PS 11 07 249 a styrene-acrylic acid resin with 30% by weight acrylic acid and a molecular weight M n of 1900 was produced.
  • binder resins prepared according to Examples 1 to 4 and comparative example were used as the binder resin X n .
  • the printing inks are applied to the various substrates using a 12 / u doctor blade.
  • the drying takes place in the warmth in order to achieve a complete evaporation of the volatile components.
  • the water resistance can be determined in accordance with DIN 16 524 or by determining the so-called wet friction resistance.
  • a damp fleece is pulled over the pressure under a load of approx. 1 kg / cm.
  • the results are assessed optically by comparing the differently colored nonwovens according to the gray scale in accordance with DIN 54 002.
  • the printing inks produced with the printing ink binders according to the invention reach level 4 while conventional ones Resins from the class of saturated polyester resins and maleate resins only reach level 3.
  • the adhesive strength of the prints is checked on polyethylene film pretreated by corona discharge, which should have a minimum surface tension of 38 dynes / cm.
  • the test is carried out according to the so-called "tesa tear test".
  • the resins according to the invention give good adhesion to polyethylene. Adhesive strength is also given on cellophane and aluminum foils.
  • the ink run-out times are around 16 to 22 seconds in a DIN cup with a 4 mm nozzle.
  • the viscosity does not increase.
  • Resins of the conventional type tend to increase in viscosity. This increase in viscosity is a significant disadvantage of conventional binders, since only printing inks with a low viscosity can be processed on the printing press.

Abstract

1. A printing ink binder based on carboxyl-containing copolymers which have been made water-dilutable by the addition of a base and have been prepared from a monomer mixture consisting of A. 25 to 50% by weight of at least one alpha,beta-olefinically unsaturated monocarboxylic acid which contains 3 to 5 carbon atoms and may, if desired, be partially replaced by alpha,beta-olefinically unsaturated dicarboxylic acids, their anhydrides and/or monoesters, B. 50 to 75% by weight of at least one vinylaromatic, and C. 0 to 10% by weight of one or more copolymerizable acrylically unsaturated monomers which are insoluble or only slightly soluble in water, with the proviso that the sum of the percentages specified under (A) to (C) is 100, by continuous mass polymerization, the residence time being < 30 minutes, at a temperature of from 200 to 400 degrees C in the absence of a free-radical-generating polymerization initiator and a regulator, and have a number-average molecular weight ~Mn of from 400 to 4 000, wherein the carboxyl-containing copolymer has a non-uniformity factor with respect to the molecular weight N = ~Mw /~Mn - 1 =< 2.

Description

Die Erfindung betrifft ein Verfahren. zur Herstellung von Druckfarbenbindemitteln durch Polymerisation eines Monomerengemisches aus Vinylaromaten und monoolefinisch ungesättigten Carbonsäuren und deren Verwendung als Bindemittel für wäßrige Druckfarben zum Bedrucken von Papier, Kunststoff- und Metallfolien.The invention relates to a method. for the production of printing ink binders by polymerizing a monomer mixture of vinyl aromatics and monoolefinically unsaturated carboxylic acids and their use as binders for aqueous printing inks for printing on paper, plastic and metal foils.

Wäßrige Druckfarben finden hauptsächlich beim Bedrucken von Papier und Wellpappe Verwendung. Erhöhte Anforderungen an die Luftreinhaltung haben zu einem steigenden Bedarf an wäßrigen Druckfarben auch für nicht saugfähige Druckträger geführt.Aqueous printing inks are mainly used for printing on paper and corrugated cardboard. Increased requirements for air pollution control have led to an increasing demand for aqueous printing inks, even for non-absorbent printing media.

Bisher wurden als gebräuchliche Bindemittel für diese Art von Druckfarben Maleinatharze, saure Polyesterharze und Acrylatharzlösungen verwendet, wie sie z.B. in den DE-OS 24 21 826; US-PS 4 166 811 sowie JP-OS 53 083 809 beschrieben sind. Nachteilig bei den bisher bekannten und auf dem Markt befindlichen Produkten ist die oftmals mangelhafte Haftfestigkeit auf vorbehandelten Polyolefinfolien, Cellglas, Aluminium und Polyesterfolien, der niedrige Glanz der Drucke und die häufig auftretenden Inhomogenitäten, die das äußere Erscheinungsbild der Drucke stören, sowie die unbefriedigende Lagerstabilität und Chargenkonstanz und die damit zusammenhängenden Schwankungen in der Viskosität der Druckfarben, die die Verarbeitung erschweren. Ferner benötigen diese Bindemittel nicht unerhebliche Mengen an organischen Lösemitteln, um überhaupt die Löslichkeit in alkalischen wäßrigen Medien zu gewährleisten.Hitherto, maleinate resins, acidic polyester resins and acrylate resin solutions have been used as common binders for this type of printing inks, e.g. in DE-OS 24 21 826; US-PS 4 166 811 and JP-OS 53 083 809 are described. Disadvantages of the products known and available on the market to date are the often inadequate adhesive strength on pretreated polyolefin films, cellophane, aluminum and polyester films, the low gloss of the prints and the frequently occurring inhomogeneities which disturb the external appearance of the prints, and the unsatisfactory storage stability and Batch consistency and the associated fluctuations in the viscosity of the printing inks, which make processing difficult. Furthermore, these binders require not insignificant amounts of organic solvents in order to ensure their solubility in alkaline aqueous media at all.

Aufgabe der Erfindung war es deshalb, ein Verfahren zur Herstellung von Druckfarbenbindemitteln aufzuzeigen, mit dem Bindemittel erhalten werden, die die obigen Nachteile nicht aufweisen. Darüber hinaus sollten diese Bindemittel im schwach alkalischen Bereich löslich und wasserverdünnbar sein. Ebenso sollte die Bindemittellösung auch bei einem nur geringen Anteil an wassermischb.aren organischen Lösungsmitteln eine niedrige Viskosität aufweisen. Die mit dem Bindemittel hergestellten Druckfarben sollten ferner eine gute Pigmentverträglichkeit, Viskositätsstabilität nach Lagerung, Geruchsneutralität und eine gute Verdruckbarkeit zeigen. Wesentliche Bedeutung kommt außerdem der Naßwischfestigkeit nach dem Trocknen der Druckfarbe und der Haftfestigkeit auf dem Substrat zu. Ferner sollte eine absolute Chargenkonstanz der wäßrigen Druckfarben gewährleistet seinThe object of the invention was therefore to provide a process for the production of printing ink binders with which binders are obtained which do not have the above disadvantages. In addition, these binders should be soluble and water-dilutable in the weakly alkaline range. Likewise, the binder solution should have a low viscosity even with only a small proportion of water-miscible organic solvents. The printing inks produced with the binder should also have good pigment compatibility, viscosity stability after storage, neutral odor and good printability. The wet wipe resistance after drying of the printing ink and the adhesive strength on the substrate are also of significant importance. Furthermore, absolute batch constancy of the aqueous printing inks should be ensured

Dieses Ziel wird überraschenderweise mit den nach dem erfindungsgemäßen Verfahren hergestellten Bindemittlen erreicht. Wesentlich für die erfindungsgemäßen Eigenschaften des sauren Harzes sind das zahlenmäßige Verhältnis der Comonomereinheiten, das Molekulargewicht und die Herstellung durch eine kontinuierliche Massepolymersation.This goal is surprisingly achieved with the binders produced by the process according to the invention. The numerical ratio of the comonomer units, the molecular weight and the production by continuous bulk polymerization are essential for the properties of the acidic resin according to the invention.

Gegenstand der vorliegenden Erfindung ist ein Verfahren zur Herstellung von Druckfarbenbindemitteln auf Basis carboxylgruppenhaltiger Copolymerisate, die durch Zusatz von Basen wasserverdünnbar sind, das dadurch gekennzeichnet ist, daß sie aus einem Monomerengemisch aus

  • (A) 25 bis 50 Gew.% mindestens einer α,β-olefinisch un-- gesättigten, 3 bis 5 Kohlenstoffatome enthaltenden Monocarbonsäure, die gegebenenfalls teilweise durch α,β-olefinisch ungesättigte Dicarbonsäuren, deren Anhydride und/oder Halbester ersetzt sein kann, (B) 50 bis 75 Gew.% mindestens eines Vinylaromaten
  • (C) 0 bis 10 Gew.% eines oder mehreren in Wasser nicht oder nur geringfügig löslichen copolymerisierbaren acrylisch ungesättigten Monomeren,
mit der Maßgabe, daß die Summe der unter (A) bis (C) genannten Prozentzahlen 100 ist, durch kontinuierliche Massepolymerisation bei Temperaturen von 200 bis 400°C in Abwesenheit von radikalliefernden Polymerisationsinitiatoren und Reglern hergestellt werden und ein mittleres Molekulargewicht M von 400 bis 4000 aufweisen.The present invention relates to a process for the preparation of printing ink binders based on copolymers containing carboxyl groups, which can be diluted with water by adding bases, which is characterized in that it consists of a monomer mixture
  • (A) 25 to 50% by weight of at least one α, β-olefinically unsaturated, 3 to 5 carbon atom-containing monocarboxylic acid, which may optionally be partially replaced by α, β-olefinically unsaturated dicarboxylic acids, their anhydrides and / or half esters, (B) 50 to 75% by weight of at least one vinylaromatic
  • (C) 0 to 10% by weight of one or more copolymerizable acrylic unsaturated monomers which are insoluble or only slightly soluble in water,
with the proviso that the sum of the percentages mentioned under (A) to (C) is 100, by continuous bulk polymerization at temperatures of 200 to 400 ° C in the absence of radical-supplying polymerization initiators and regulators and an average molecular weight M of 400 to 4000 exhibit.

Vorzugsweise wird die kontinuierliche Massepolymerisation des Monomerengemisches bei Verweilzeiten von < 30 Minuten durchgeführt. Bevorzugt sind insbesondere auch solche erfindungsgemäß hergestellten Druckfarbenbindemittel, die einen Uneinheitlichkeitsfaktor bezüglich des Molekulargewichts U = Mw/Mn - 1< 2 aufweisen. Gegenstand der vorliegenden Erfindung ist außerdem die Verwendung der erfindungsgemäß hergestellten carboxylgruppenhaltigen Copolymerisate als Bindemittel für wäßrige Druckfarben zum Bedrucken von Papier, Kunststoff- und Metallfolien.The continuous bulk polymerization of the monomer mixture is preferably carried out with residence times of <30 minutes. Printing ink binders which are produced according to the invention and which have a non-uniformity factor with regard to the molecular weight U = M w / M n −1 <2 are particularly preferred. The present invention also relates to the use of the copolymers containing carboxyl groups prepared according to the invention as binders for aqueous printing inks for printing on paper, plastic and metal foils.

Aus der DE-OS 25 02 172 sind Harze bekannt, die u.a. durch thermische Copolymerisation - also ohne radikalbildende Initiatoren - von 2 bis 25 Gew.% Acrylsäure, Styrol und Maleinsäureanhydrid bei ca. 150 bis 300°C erhalten werden. Diese Harze sind schwer oder überhaupt nicht alkalilöslich und werden gemäß der genannten Publikation als Papierleimungsmittel empfohlen. Sie eignen sich jedoch nicht als Harzkomponente für die Bindemittellösung wäßriger Druckfarben, da sie eine zu geringe Wasserlöslichkeit und Haftfestigkeit auf nicht saugfähigen Druckträgern aufweisen.Resins are known from DE-OS 25 02 172, which among other things. by thermal copolymerization - that is to say without free-radical initiators - from 2 to 25% by weight of acrylic acid, styrene and maleic anhydride at about 150 to 300 ° C. These resins are poorly or not at all alkali-soluble and are recommended as paper sizes according to the publication mentioned. However, they are not suitable as a resin component for the binder solution of aqueous printing inks, since they have insufficient water solubility and adhesive strength on non-absorbent print media.

In der DE-AS 15 19 201 und GB-PS 11 07 249 werden alkalilösliche Harze beschrieben, die sich aus Styrol und (Meth)acrylsaure als Comonomere aufbauen und als alkalilösliche Harze für Polymerdispersionen eingesetzt werden. Diese Harzkomponenten werden durch Lösungspolymerisation in Gegenwart von radikalbildenden Initiatoren und Reglern in diskontinuierlicher Fahrweise erhalten. Der Nachteil solcher Harze ist, daß sie als Bindemittel in wäßrigen Druckfarben eine zu geringe Haftung auf Polymer- und Metallfolien ergeben, so daß die Naßwischfestigkeit der Druckfarben zu wünschen übrig läßt. In diesen Patentschriften findet sich dementsprechend auch kein Hinweis auf die Verwendung dieser Harze als Bindemittel für wäßrige Druckfarben.DE-AS 15 19 201 and GB-PS 11 07 249 describe alkali-soluble resins which are composed of styrene and (meth) acrylic acid as comonomers and are used as alkali-soluble resins for polymer dispersions. These resin components are obtained by solution polymerization in the presence of free radical initiators and regulators in a batchwise manner. The disadvantage of such resins is that they give too little adhesion to polymer and metal foils as binders in aqueous printing inks, so that the wet wipe resistance of the printing inks leaves something to be desired. Accordingly, there is no reference in these patents to the use of these resins as binders for aqueous printing inks.

Die erfindungsgemäßen sauren Harze weisen jedoch diese Nachteile nicht auf. Es ist überraschend, daß im Hinblick auf das diskontinuierlich hergestellte Harz der DE-AS 15 19 201 durch kontinuierliche, rein thermisch ausgeführte Massepolymerisation bei Temperaturen von 200 --bis 400°C und niedrigen Verweilzeiten Produkte mit an sich ähnlichem Aufbau, aber für die Verwendung als Bindemittel in wäßrigen Druckfarben wesentlich verbesserten Eigenschaften insbesondere bezüglich der Haftfestigkeit auf nichtsaugfähigen Druckträgern, der Naßwischfestigkeit und der Lagerstabilität, erhalten werden.However, the acidic resins according to the invention do not have these disadvantages. It is surprising that with regard to the discontinuously produced resin of DE-AS 15 19 201 by continuous, purely thermal bulk polymerization at temperatures from 200 ° to 400 ° C. and low residence times, products with a structure that is similar per se, but for use As a binder in aqueous printing inks, substantially improved properties, in particular with regard to the adhesive strength on non-absorbent printing media, the wet smear resistance and the storage stability, can be obtained.

Darüber hinaus wurde überraschenderweise gefunden, daß die neuen Bindemittelharze bei der Verarbeitung der damit hergestellten wäßrigen Druckfarben zu glänzenden Drucken mit makelloser Oberfläche führen.In addition, it was surprisingly found that the new binder resins lead to glossy prints with a flawless surface when processing the aqueous printing inks produced therewith.

Zu den Aufbaukomponenten, die für das erfindungsgemäße Verfahren zur Herstellung von Druckfarbenbindemitteln zu verwenden sind, ist im einzelnen folgendes auszuführen:

  • (A) Als α,β-olefinisch ungesättigte, 3 bis 5 Kohlenstoffatome enthaltende Monocarbonsäuren kommen beispielsweise Acrylsäure und Methacrylsäure in Frage. Die Monocarbonsäuren können teilweise, bis zu 50, vorzugsweise bis zu 25 Gewichtsprozent durch α,β-olefinisch ungesättigte Dicarbonsäuren, wie z.B. Maleinsäure, Fumarsäure, deren Anhydride, wie z.B. Maleinsäureanhydrid und/oder Halbester, wie z.B. Maleinsäure- oder Fumarsäurehalbester von 1 bis 8 Kohlenstoffatome enthaltenden Alkoholen ersetzt sein. Komponente (A) ist im Monomerengemisch im allgemeinen in einer Menge von 25 bis 50, vorzugsweise 30 bis 45 Gewichtsprozent, bezogen auf die Gesamtmenge der Monomeren (A) + (B) + (C) enthalten, bzw. im Copolymerisat einpolymerisiert.
  • (B) Als Vinylaromaten kommen in Frage Styrol, Vinyltoluol, α-Methylstyrol oder höher substituierte Styrole, wie z.B. 2,4-Dimethylstyrol. Bevorzugt sind Styrol, Vinyltoluol und α-Methylstyrol. Komponente (B) ist im Monomeren-Gemisch im allgemeinen in einer Menge von 50 bis 75, vorzugsweise 55 bis 70 Gewichtsprozent, bezogen auf die Gesamtmenge der Monomeren (A) + (B) + (C) enthalten, bzw. im Copoiymerisat einpolymerisiert.
  • (C) Als weitere in Wasser nicht oder nur geringfügig lösliche copolymerisierbare acrylisch ungesättigte Monomeren kommen in Frage Ester der Acrylsäure oder Methacrylsäure mit 1 bis 8, vorzugsweise 1 bis 4 Kohlenstoffatome enthaltenden Monoalkanolen, die gegegebenenfalls Äthergruppen enthalten können.
Regarding the structural components that are to be used for the process according to the invention for the production of printing ink binders, the following must be carried out in detail:
  • (A) Examples of suitable α, β-olefinically unsaturated monocarboxylic acids containing 3 to 5 carbon atoms are acrylic acid and methacrylic acid. The monocarboxylic acids can contain up to 50, preferably up to 25 percent by weight of α, β-olefinically unsaturated dicarboxylic acids, such as maleic acid, fumaric acid, their anhydrides, such as maleic anhydride and / or half esters, such as maleic or fumaric acid semiesters from 1 to 8 Alcohols containing carbon atoms may be replaced. Component (A) is generally present in the monomer mixture in an amount of 25 to 50, preferably 30 to 45 percent by weight, based on the total amount of monomers (A) + (B) + (C), or copolymerized in the copolymer.
  • (B) Suitable vinyl aromatics are styrene, vinyl toluene, α-methylstyrene or styrenes with higher substitution, such as, for example, 2,4-dimethylstyrene. Styrene, vinyltoluene and α-methylstyrene are preferred. Component (B) is generally present in the monomer mixture in an amount of 50 to 75, preferably 55 to 70 percent by weight, based on the total amount of monomers (A) + (B) + (C), or copolymerized in the copolymer.
  • (C) Other suitable copolymerizable acrylic unsaturated monomers which are insoluble or only slightly soluble in water are esters of acrylic acid or methacrylic acid with 1 to 8, preferably 1 to 4, carbon atoms-containing monoalkanols, which may optionally contain ether groups.

Nitrile, wie z.B. Acrylnitril-oder Methacrylnitril, Amide, wie Acrylamid oder Maleinsäure- oder Fumarsäuredialkylester von 1 bis 8 C-Atome enthaltenden Alkoholen. Bevorzugte Monomere (C) sind z.B. n-Butylacrylat, Methylmethacrylat und/oder Acrylnitril.Nitriles, e.g. Acrylonitrile or methacrylonitrile, amides, such as acrylamide or maleic acid or fumaric acid dialkyl esters of alcohols containing 1 to 8 carbon atoms. Preferred monomers (C) are e.g. n-butyl acrylate, methyl methacrylate and / or acrylonitrile.

Diese Monomeren (C) können im Monomergemisch bis zu 10, vorzugsweise 2 bis 7 Gewichtsprozent, bezogen auf die Gesamtmenge der Monomeren (A) + (B) + (C) enthalten sein, bzw. im Copolymerisat einpolymerisiert sein.These monomers (C) can be present in the monomer mixture up to 10, preferably 2 to 7 percent by weight, based on the total amount of monomers (A) + (B) + (C), or copolymerized in the copolymer.

Bevorzugt sind Copolymerisate, die Acrylsäure und/oder Methacrylsäure als Komponente (A) und Styrol und/oder Vinyltoluol als Komponente (B) einpolymerisiert enthalten, wobei die Komponente (A) auch Maleinsäure- oder Fumarsäureeinheiten enthalten kann.Copolymers which contain acrylic acid and / or methacrylic acid as component (A) and styrene and / or vinyltoluene as component (B) are preferred, component (A) also being able to contain maleic acid or fumaric acid units.

Erfindungsgemäß wird die Copolymerisation kontinuierlich bei Temperaturen zwischen 200 und 400, vorzugsweise zwischen 220 und 380°C und in Abwesenheit von radikalbildenden Initiatoren und Reglern durchgeführt. Ein Copolymerisat aus Styrol, Acrylsäure kann beispielsweise.dadurch hergestellt werden, daß man die Monomeren einem Reaktor oder zwei hintereinandergeschalteten Polymerisationszonen, beispielsweise einer Druckkesselkaskade, kontinuierlich zuführt und nach einer Verweilzeit von 3 bis 30, vorzugsweise 5 bis 25 Min. bei Temperaturen zwischen 200 und 400°C kontinuierlich aus der Reaktionszone ausschleust. Die Einhaltung dieser Temperaturgrenzen ist wichtig, da bei Unterschreiten die Verweilzeiten zu lang'und die Molgewichte zu hoch werden, und bei Überschreitung thermische Zersetzungsprozesse eintreten können.According to the invention, the copolymerization is carried out continuously at temperatures between 200 and 400, preferably between 220 and 380 ° C. and in the absence of free radical initiators and regulators. A copolymer of styrene and acrylic acid can be prepared, for example, by continuously feeding the monomers to a reactor or two series-connected polymerization zones, for example a pressure vessel cascade, and after a residence time of 3 to 30, preferably 5 to 25, minutes at temperatures between 200 and 400 ° C continuously discharged from the reaction zone. It is important to keep to these temperature limits, as the dwell times are too long and the molecular weights too high if the temperature is too low, and thermal decomposition processes can occur if they are exceeded.

Als Polymerisationsapparatur kann z.B. ein Druckkessel, eine Druckkesselkaskade, ein Druckrohr oder auch ein Druck- kessel mit einem nachgeschalteten Reaktionsrohr, das mit einem statischen Mischer versehen ist, verwendet werden. Vorzugsweise polymerisiert man das Monomerengemisch (A) + (B) + gegebenenfalls (C) in mindestens zwei hintereinander geschalteten Polymerisationszonen. Dabei kann die eine Reaktionszone aus einem druckdichten Kessel, die andere aus einem druckdichten Reaktionsrohr, vorzugsweise einem beheizbaren statischen Mischer bestehen. Wenn man die Polymerisation in zwei hintereinandergeschalteten Zonen durchführt, erhält man Umsätze, die oberhalb 99 % liegen. Während der Polymerisation muß für eine gute Durchmischung der Komponenten gesorgt werden, beispielsweise verwendet man druckdichte Kessel, die mit einem Rührer ausgestattet sind, oder Polymerisationsrohre mit statischen Mischern.A polymerization vessel, a pressure vessel cascade, a pressure tube or a pressure boilers with a downstream reaction tube equipped with a static mixer can be used. The monomer mixture (A) + (B) + optionally (C) is preferably polymerized in at least two polymerization zones connected in series. One reaction zone can consist of a pressure-tight vessel, the other of a pressure-tight reaction tube, preferably a heatable static mixer. If the polymerization is carried out in two zones connected in series, conversions are obtained which are above 99%. During the polymerization, thorough mixing of the components must be ensured, for example using pressure-tight vessels which are equipped with a stirrer, or polymerization tubes with static mixers.

Die Polymerisation kann bei Drücken von > 1 bar, vorzugsweise zwischen 1 und 200 bar durchgeführt werden. Besonders gute Ergebnisse erhält man, wenn man die Polymerisationsreaktion bei periodischen Druckschwankungen mit Druckdifferenzen zwischen 5 und 120 bar durchführt und anschließend ebenfalls bei periodischen Druckschwankungen mit denselben Druckdifferenzen entspannt. Diese Maßnahme, die eine pulsierende Strömung des Reaktionsgutes zur Folge hat, bewirkt eine Selbstreinigung des Reaktors und verhindert produktschädigende Wandbeläge und Anbackungen im Reaktor. Der Produktaustrag ist homogen und enthält keine Stippen oder vercracktes Material.The polymerization can be carried out at pressures of> 1 bar, preferably between 1 and 200 bar. Particularly good results are obtained if the polymerization reaction is carried out with periodic pressure fluctuations with pressure differences between 5 and 120 bar and then also relaxed with periodic pressure fluctuations with the same pressure differences. This measure, which results in a pulsating flow of the reaction material, causes the reactor to self-clean and prevents product-damaging wall coverings and caking in the reactor. The product discharge is homogeneous and contains no specks or cracked material.

Unter kontinuierlicher Polymerisation im Sinne der vorliegenden Erfindung soll auch eine Arbeitsweise verstanden werden, bei der in einer Polymerisationszone, z.B. in einem Kessel, zunächst etwa 10 % der Monomeren-Mischung vorgelegt wird und bei der man dann anschließend den Rest der Monomeren-Mischung kontinuierlich im Verlauf von 10 bis 30 Min. zulaufen läßt. Bei dieser Verfahrensvariante liegen jedoch die Raumzeitausbeuten nicht so hoch wie bei dem kontinuierlichen Polymerisieren in zwei hintereinandergeschalteten Reaktionszonen. Im Gegensatz zu den bekannten Verfahren wird vorzugsweise in Abwesenheit eines Lösungsmittels polymerisiert. Bei entsprechender Wahl der Monomerenzusammensetzung und der Einsatzmenge an Monomeren pro Zeiteinheit, reicht die bei der Polymerisation freiwerdende Wärmemenge aus, um die für die Polymerisation erforderliche Temperatur aufrechtzuerhalten. Gelegentlich kann es jedoch erforderlich sein, die Reaktionszone zu beheizen bzw. zu kühlen. In Abhängigkeit von der Polymerisationstemperatur und der Verweilzeit der Reaktionsmischung in der Polymerisationszone erhält man Umsätze an Monomeren, die oberhalb von 99, vorzugsweise mehr als 99,5 5 betragen. Die nach dem erfindungsgemäßen Verfahren hergestellten Copolymerisate enthalten daher nur noch so geringe Mengen unumgesetzter Monomerer, daß es in aller Regel nicht erforderlich ist, die restlichen geringen Mengen an Monomeren aus dem Polymerisat zu entfernen.Continuous polymerization for the purposes of the present invention should also be understood to mean a procedure in which about 10% of the monomer mixture is initially introduced in a polymerization zone, for example in a kettle, and in which the rest of the monomer mixture is then subsequently introduced continuously Course of 10 up to 30 minutes. In this process variant, however, the space-time yields are not as high as in the case of continuous polymerization in two reaction zones connected in series. In contrast to the known methods, polymerization is preferably carried out in the absence of a solvent. With appropriate selection of the monomer composition and the amount of monomers used per unit of time, the amount of heat released during the polymerization is sufficient to maintain the temperature required for the polymerization. Occasionally, however, it may be necessary to heat or cool the reaction zone. Depending on the polymerization temperature and the residence time of the reaction mixture in the polymerization zone, conversions of monomers are obtained which are above 99, preferably more than 99.5. The copolymers prepared by the process according to the invention therefore only contain such small amounts of unconverted monomers that it is generally not necessary to remove the remaining small amounts of monomers from the polymer.

Sollte es jedoch zur völligen Vermeidung von Geruchsbelästigungen notwendig sein, noch enthaltene flüchtige Bestandteile zu entfernen, so kan das Polymerisat im Vakuum entgast werden. Hierzu werden bekannte Verdampfungsaggregate, wie Rohrverdampfer, Plattenverdampfer oder Filmtruder eingesetzt. In der Regel ist ein solcher Entgasungsschritt für die Herstellung der erfindungsgemäßen Polymerisate jedoch nicht notwendig.However, if it is necessary to completely remove any volatile constituents to completely avoid odor nuisance, the polymer can be degassed in vacuo. Known evaporation units such as tube evaporators, plate evaporators or film extruders are used for this purpose. As a rule, however, such a degassing step is not necessary for the production of the polymers according to the invention.

Das Molekulargewicht der erfindungsgemäß hergestellten Copölymerisate beträgt 400 bis 4000, vorzugsweise 500 bis 2000. Es kann einerseits über die Polymerisationstemperatur, andererseits über die Verweilzeit gesteuert werden.The molecular weight of the copolymers prepared according to the invention is 400 to 4000, preferably 500 to 2000. It can be controlled on the one hand via the polymerization temperature and on the other hand via the residence time.

'Das Copolymerisat kann aus der Polymerisationsapparatur kontinuierlich z.B. über ein Entspannungsgefäß mit nachgeschaltetem Austragsaggregat oder vorzugsweise pulsierend ausgetragen werden. Beim Einsatz gekühlter Transportbänder erhält man somit dünnwandiges Festprodukt, das sich aufgrund der großen Oberfläche in alkalischem Medium schnell auflöst. Für viele Anwendungen ist es zweckmäßig, das Copolymerisat in teilneutralisierter zumindest aber in gelöster Form einzusetzen. Die Carboxylgruppen des Copolymerisates werden daher in diesen Fällen im Anschluß an die Polymerisation mit Basen teilweise, bzw. bis zu 100 % neutralisiert.'' The copolymer can be continuously extracted from the polymerization apparatus e.g. are discharged via a relaxation vessel with a downstream discharge unit or preferably in a pulsating manner. When using cooled conveyor belts, you get a thin-walled solid product that quickly dissolves in an alkaline medium due to the large surface area. For many applications it is expedient to use the copolymer in partially neutralized or at least in dissolved form. The carboxyl groups of the copolymer are therefore partially or up to 100% neutralized in these cases following the polymerization with bases.

Geeignete Basen sind beispielsweise gasförmiges Ammoniak, wäßrige Ammoniaklösungen oder wäßrige Lösungen anderer Basen wie Natronlauge, Kalilauge, Erdalkalihydroxide, wie Magnesiumhydroxid und Calciumhydroxid oder Amine, wie Monoalkylamine, Dialkylamine und Trialkylamine oder Mischungen der Amine sowie Alkanolamine, wie z.B. Dimethylethanolamin. Bei der Neutralisation wird in der Regel so verfahren, daß Copolymerisatlösungen anfallen, die einen Feststoffgehalt zwischen 10 und 40 Gew.% aufweisen. Die wäßrigen, teil- oder vollständig neutralisierten Copolymerisatlösungen können durch Zugabe von Wasser leicht verdünnt werden. Die wäßrige Lösung kann gegebenenfalls auch noch bis zu 10 Gew.% eines Alkanols mit 1 - 4 C-Atomen enthalten. Beispiele für solche Alkanole sind Methanol, Ethanol, iso-Propanol und n-Butanol; bevorzugt eingesetzt wird Iso-Propanol.Suitable bases are, for example, gaseous ammonia, aqueous ammonia solutions or aqueous solutions of other bases such as sodium hydroxide solution, potassium hydroxide solution, alkaline earth metal hydroxides such as magnesium hydroxide and calcium hydroxide or amines such as monoalkylamines, dialkylamines and trialkylamines or mixtures of the amines and alkanolamines such as e.g. Dimethylethanolamine. Neutralization is generally carried out in such a way that copolymer solutions are obtained which have a solids content of between 10 and 40% by weight. The aqueous, partially or completely neutralized copolymer solutions can easily be diluted by adding water. If appropriate, the aqueous solution can also contain up to 10% by weight of an alkanol having 1 to 4 carbon atoms. Examples of such alkanols are methanol, ethanol, isopropanol and n-butanol; Isopropanol is preferably used.

Die Lösung der Bindemittelharze kann jedoch auch direkt im Anschluß an die Copolymerisation kontinuierlich durchgeführt werden. Die aus dem Reaktor kommende heiße Polymerisatschmelze wird dann bei Temperaturen von 80 bis 200oC, Drücken oberhalb 1 bar und Verweilzeiten von 5 bis 30 Minuten gelöst. Als Lösungsapparaturen können z.B. Druckkessel, Druckrohre, die ggf. Mischorgane eingebaut enthalten oder auch Kombinationen von Druckkesseln und Druckrohren verwendet werden. Vorzugsweise werden Kombinationen von Druckrohren benutzt, die mindestens teilweise mit Mischorganen ausgestattet sind. Diese Organe können Stäbe oder Siebplatten sein.However, the binder resins can also be dissolved continuously immediately after the copolymerization. The hot polymer melt coming from the reactor is then dissolved at temperatures of 80 to 200 ° C., pressures above 1 bar and residence times of 5 to 30 minutes. As solution apparatus can eg pressure vessels, pressure pipes, which may contain built-in mixing elements, or combinations of pressure vessels and pressure pipes may also be used. Combinations of pressure pipes are preferably used which are at least partially equipped with mixing elements. These organs can be rods or sieve plates.

Vorzugsweise verwendt man solche Mischorgane, die die Reaktionsmasse bei möglichst geringem Strömungswiderstand in verschiedene Ströme zerteilen und unter Veränderung der Strömungsrichtung wieder zusammenführen. Beispiele für solche Mischelemente sind statische Mischer. Der Inhalt des Reaktorsystems ist im allgemeinen so bemessen, daß bei der gegebenen Verweilzeit von 5 bis 30 Minuten ebenfalls hohe Raum-Zeit-Ausbeuten, z.B. in dem Bereich von 1 bis 50 kg Copolymerisat pro Liter und Stunde erzielt werden. Das teilneutralisierte bzw. vollständig neutralisierte Copolymerisat wird in der bevorzugten Ausführungsform des Verfahrens aus der Polymerisationsvorrichtung unter pulsierender Entspannung ausgetragen. Der Druck beim Lösevorgang beträgt mehr als 1 bar und liegt vorzugsweise in dem Bereich von 5 bis 120 bar. Die wäßrigen Druckfarben enthalten im allgemeinen eine Bindemittellösung die aufgebaut ist ausMixing elements are preferably used which break the reaction mass into different streams with the lowest possible flow resistance and bring them together again by changing the flow direction. Examples of such mixing elements are static mixers. The content of the reactor system is generally such that, given the residence time of 5 to 30 minutes, high space-time yields, e.g. can be achieved in the range of 1 to 50 kg copolymer per liter and hour. In the preferred embodiment of the process, the partially neutralized or completely neutralized copolymer is discharged from the polymerization device with pulsating relaxation. The pressure during the dissolving process is more than 1 bar and is preferably in the range from 5 to 120 bar. The aqueous printing inks generally contain a binder solution which is composed of

Figure imgb0001
Lösungen dieser Konzentration und Zusammensetzung weisen eine Auslaufzeit von 10 - 30 Sekunden im Auslaufbecher nach DIN 53 211 auf.
Figure imgb0001
 Solutions of this concentration and composition have a flow time of 10 - 30 seconds in the flow cup according to DIN 53 211.

Die nach dem erfindungsgemäßen Verfahren hergestellten Bindemittel ergeben Druckfarben gleichbleibender Qualität, hinsichtlich der Lagerbeständigkeit, Glanzgebung, Haftfestigkeit, Verhalten auf der Druckmaschine und insbesondere Naßwischfestigkeit und Geruchsneutralität. Sie eignen sich außer für den Flexodruck auch für wäßrigen Tiefdruck.The binders produced by the process according to the invention result in printing inks of constant quality, with regard to storage stability, gloss, adhesive strength, behavior on the printing press and in particular wet wiping resistance and odor neutrality. In addition to flexographic printing, they are also suitable for aqueous gravure printing.

Die Pigmente, die zur Herstellung der Druckfarben verwendet werden, können aus den üblichen Pigmenten ausgewählt werden, die für Tiefdruck- oder Flexodruckfarben brauchbar sind.The pigments used to make the inks can be selected from the usual pigments that are useful for gravure or flexographic inks.

Zur Verbesserung der Reibbeständigkeit eines aus dem erfindungsgemäßen Bindemittel hergestellten Druckfilms können der Druckfarbe zusätzlich noch mikrokristallines Wachs, Polyethylenwachs u.U. als wäßrige Dispersion, oder auch andere für Druckfarben übliche Modifizierungsmittel zugesetzt werden.To improve the rub resistance of a printing film made from the binder according to the invention, the printing ink can additionally microcrystalline wax, polyethylene wax may. as an aqueous dispersion, or other modifiers customary for printing inks can be added.

Die Bindemittellösungen werden den wäßrigen Druckfarben im allgemeinen zu -40 - 90 Gew.%, vorzugsweise 45 - 80 Gew.% zugesetzt. Die Mischung mit Pigmentpräparationen oder das Anreiben mit anorganischen und organischen Pigmenten kann mit den üblichen Misch- bzw. Anreibeaggregaten durchgeführt werden. Besonders vorteilhaft ist; wenn man Pigmente verwendet, die in einem besonderen Finishprozeß für die Dispergierung in wäßrigen Medien ausgerüstet wurden oder wäßrige Pigmentpräparationen.The binder solutions are generally added to the aqueous printing inks at -40-90% by weight, preferably 45-80% by weight. Mixing with pigment preparations or rubbing with inorganic and organic pigments can be carried out with the usual mixing or rubbing aggregates. It is particularly advantageous; when using pigments which have been equipped in a special finishing process for dispersion in aqueous media or aqueous pigment preparations.

Die in den Beispielen genannten Teile und Prozente beziehen sich auf das Gewicht.The parts and percentages given in the examples relate to the weight.

I. Erfindungsgemäße Herstellung der DruckfarbenbindemittelsI. Production of the Ink Binder According to the Invention Beispiel 1example 1 Bindemittelharz X1 Binder resin X 1

60 Teile Styrol und 40 Teile Acrylsäure wurden in einen 1000 Teile fassenden Druckkessel mit nachgeschaltetem Druckrohr doppelten Rauminhalts mit Druckregler kontinuierlich zudosiert. Das System wurde auf 310°C erhitzt. Der Druck wurde im Bereich zwischen 5 und 50 bar gehalten und einmal innerhalb einer Minute durch eine periodische Druckregelung in diesem Bereich variiert. Die Verweilzeit betrug 11 Min.; die Copolymerschmelze wurde mengenmäßig in dem Maße ausgefahren, wie frische Monomerenmischung zugefahren wurde. Das Copolymerisat wies ein mittleres Molekulargewicht Mn von 650 und eine Molekulargewichtsuneinheitlichkeit U = Mw/In-1 von 1,5 auf.60 parts of styrene and 40 parts of acrylic acid were metered in continuously into a 1000 part pressure vessel with a pressure tube connected downstream and twice the volume with a pressure regulator. The system was heated to 310 ° C. The pressure was kept in the range between 5 and 50 bar and varied once in one minute by periodic pressure regulation in this range. The dwell time was 11 minutes; the copolymer melt was drawn out in quantity to the extent that fresh monomer mixture was fed in. The copolymer had an average molecular weight M n of 650 and a molecular weight nonuniformity U = M w / I n -1 of 1.5.

Beispiel 2Example 2 Bindemittelharz X2Binder resin X2

70 Teile Styrol und 30 Teile Acrylsäure wurden gemäß Beispiel 1 copolymerisiert. Die Temperatur betrug 290oC, die Verweilzeit 15 Minuten und der Druck zwischen 5 und 60 bar.70 parts of styrene and 30 parts of acrylic acid were copolymerized in accordance with Example 1. The temperature was 290 ° C., the residence time 15 minutes and the pressure between 5 and 60 bar.

Das erhaltene Copolymerisat wies ein mittleres Molekulargewicht Mn von 870 und eine Molekulargewichtsuneinheitlich- keit von U = Mw/Mn-1 von 1,8 auf.The copolymer obtained had an average molecular weight M n of 870 and a Molekulargewichtsuneinheitlich- speed of U = M w / M n -1 of 1 to 8.

Beispiel 3Example 3 Bindemittelharz X3 Binder resin X 3

60 Teile Styrol, 34 Teile Acrylsäure und 6 Teile Methylacrylat wurden gemäß Beispiel 1 copolymerisiert. Die Temperatur betrug 300°C, der Druck 10 bis 80 bar und die Verweilzeit 9 Minuten.60 parts of styrene, 34 parts of acrylic acid and 6 parts of methyl acrylate were copolymerized in accordance with Example 1. The temperature was 300 ° C, the pressure 10 to 80 bar and the residence time 9 minutes.

Das erhaltene Copolymerisat wies ein mittleres Molgewicht Mn von 620 und eine Molekulargewichtsuneinheitlichkeit U = Mw/Mn-1 = 2,0 auf.The copolymer obtained had an average molecular weight M n of 620 and a molecular weight nonuniformity U = M w / M n -1 = 2.0.

Beispiel 4Example 4 Bindemittelharz X4 Binder resin X 4

60 Teile Styrol, 35 Teile Acrylsäure und 5 Teile Maleinsäureanhydrid wurden gemäß Beispiel 1 polymerisiert. Die Temperatur lag bei 280°C, der Druck betrug 20 - 60 bar, die Verweilzeit 10 Minuten.60 parts of styrene, 35 parts of acrylic acid and 5 parts of maleic anhydride were polymerized according to Example 1. The temperature was 280 ° C, the pressure was 20-60 bar, the residence time was 10 minutes.

Das erhaltene Bindemittelharz X4 wies ein mittleres Molekulargewicht von Mn von 1070 auf und besaß eine Molekulargewichtsuneinheitlichkeit von 2,0.The binder resin X 4 obtained had an average molecular weight of M n of 1070 and had a molecular weight non-uniformity of 2.0.

VergleichsbeispielComparative example Vergleichsbindemittel XA Comparative binder X A

Gemäß Beispiel 1 der GB-PS 11 07 249 wurde ein Styrol-Acrylsäure-Harz mit 30 Gew.% Acrylsäure und einem Molekulargewicht Mn von 1900 hergestellt. Die Molekulargewichtsuneinheitlichkeit betrug U = Mw/Mn-1>2.According to Example 1 of GB-PS 11 07 249, a styrene-acrylic acid resin with 30% by weight acrylic acid and a molecular weight M n of 1900 was produced. The molecular weight non-uniformity was U = M w / M n -1> 2.

II. Anwendungsbeispiele:

  • Es wurden unterschiedlich zusammengesetzte wäßrige Druckfarben für den Flexodruck und den wäßrigen Tiefdruck nachfolgender Rezeptur hergestellt und vergleichend geprüft:
  • 20 Gew.% einer wäßrigen Pigmentpräparation
  • wurden mit 80 Gew.% einer Bindemittellösung bei Raumtemperatur durch Rühren vermischt. Die Bindemittellösung war aufgebaut aus:
    Figure imgb0002
II. Examples of use:
  • Different compositions of aqueous printing inks for flexographic printing and aqueous gravure printing using the following recipe were produced and compared:
  • 20% by weight of an aqueous pigment preparation
  • were mixed with 80% by weight of a binder solution at room temperature by stirring. The binder solution was made up of:
    Figure imgb0002

Als Bindemittelharz Xn wurden die gemäß Beispiele 1 bis 4 und Vergleichsbeispiel hergestellten Bindemittelharze eingesetzt.The binder resins prepared according to Examples 1 to 4 and comparative example were used as the binder resin X n .

Zur anwendungstechnischen Prüfung werden die Druckfarben mit einer 12/u Rakel auf die verschiedenen Substrate aufgetragen. Die Trocknung erfolgt in der Wärme, um eine möglichst vollständige Verdunstung der flüchtigen Anteile zu erreichen. Die Bestimmung der Wasserfestigkeit kann nach DIN 16 524 erfolgen oder durch Bestimmung der sog. Naßreibfestigkeit. Bei dieser Methode wird ein feuchtes Vlies unter Belastung von ca. 1 kg/cm über den Druck gezogen. Die Beurteilung der Ergebnisse erfolgt optisch durch den Vergleich der unterschiedlich angefärbten Vliese nach dem Graumaßstab gemäß DIN 54 002. Die mit den erfindungsgemäßen Druckfarbenbindemitteln hergestellten Druckfarben erreichen bei diesem Test die Stufe 4 während herkömmliche Harze aus der Klasse der gesättigten Polyesterharze und Maleinatharze nur die Stufe 3 erreichen.For technical application testing, the printing inks are applied to the various substrates using a 12 / u doctor blade. The drying takes place in the warmth in order to achieve a complete evaporation of the volatile components. The water resistance can be determined in accordance with DIN 16 524 or by determining the so-called wet friction resistance. With this method, a damp fleece is pulled over the pressure under a load of approx. 1 kg / cm. The results are assessed optically by comparing the differently colored nonwovens according to the gray scale in accordance with DIN 54 002. In this test, the printing inks produced with the printing ink binders according to the invention reach level 4 while conventional ones Resins from the class of saturated polyester resins and maleate resins only reach level 3.

Die Haftfestigkeit der Drucke wird auf durch Coronaentladung vorbehandelter Polyethylenfolie, die eine Mindestoberflächenspannung von 38 dyn/cm aufweisen soll, geprüft. Die Prüfung erfolgt nach dem sogenannten "Tesaabrißtest". Im Vergleich zu den herkömmlichen Harzen aus der Klasse der gesättigten Polyester, der Maleinatharze und der Acrylatharze ergeben die erfindungsgemäßen Harze eine gute Haftfestigkeit auf Polyethylen. Haftfestigkeit ist auch auf Zellglas- und Aluminiumfolien gegeben.The adhesive strength of the prints is checked on polyethylene film pretreated by corona discharge, which should have a minimum surface tension of 38 dynes / cm. The test is carried out according to the so-called "tesa tear test". In comparison to the conventional resins from the class of saturated polyesters, maleate resins and acrylate resins, the resins according to the invention give good adhesion to polyethylene. Adhesive strength is also given on cellophane and aluminum foils.

Die Auslaufzeiten der Druckfarben liegen bei etwa 16 bis 22 Sekunden im DIN-Becher mit 4 mm Düse. Nach einer Lagerung der Druckfarben bei 50°C über 3 Tage steigt die Viskosität nicht an. Harze der herkömmlichen Art neigen zum Ansteigen der Viskosität. Dieser Viskositätsanstieg ist ein bedeutender Nachteil der herkömmlichen Bindemittel, da auf den Druckmaschinen nur Druckfarben verarbeitet werden können, die eine niedrige Viskosität aufweisen.The ink run-out times are around 16 to 22 seconds in a DIN cup with a 4 mm nozzle. After storing the printing inks at 50 ° C for 3 days, the viscosity does not increase. Resins of the conventional type tend to increase in viscosity. This increase in viscosity is a significant disadvantage of conventional binders, since only printing inks with a low viscosity can be processed on the printing press.

Claims (4)

1. Verfahren zur Herstellung von Druckfarbenbindemitteln auf Basis carboxylgruppenhaltiger Copolymerisate, die durch Zusatz von Basen wasserverdünnbar sind, dadurch gekennzeichnet, daß sie aus einem Monomerengemisch aus (A) 25 bis 50 Gew.% mindestens einer α,β-olefinisch ungesättigten, 3 bis 5 Kohlenstoffatome enthaltenden Monocarbonsäure, die gegebenenfalls teilweise durch α,β-olefinisch ungesättigte Dicarbonsäuren, deren Anhydride und/oder Halbester ersetzt sein kann, (B) 50 bis 75 Gew.% mindestens eines Vinylaromaten und (C) 0 bis 10 Gew.% eines oder mehreren in Wasser nicht oder nur geringfügig löslichen copolymerisierbaren acrylisch ungesättigten Monomeren,mit der Maßgabe, daß die Summe der unter (A) bis (C) genannten Prozentzahlen 100 ist, durch kontinuierliche Massepolymerisation bei Temperaturen von 200 bis 400°C in Abwesenheit von radikalliefernden Polymerisationsinitiatoren und Reglern hergestellt werden und ein mittleres Molekulargewicht M von 400 bis 4000 aufweisen.1. A process for the preparation of printing ink binders based on carboxyl-containing copolymers which are water-dilutable by adding bases, characterized in that they consist of a monomer mixture (A) 25 to 50% by weight of at least one α, β-olefinically unsaturated monocarboxylic acid containing 3 to 5 carbon atoms, which may optionally be partly replaced by α, β-olefinically unsaturated dicarboxylic acids, their anhydrides and / or half esters, (B) 50 to 75% by weight of at least one vinylaromatic and (C) 0 to 10% by weight of one or more copolymerizable acrylic unsaturated monomers which are insoluble or only slightly soluble in water, with the proviso that the sum of the percentages mentioned under (A) to (C) is 100, by continuous bulk polymerization at temperatures of 200 to 400 ° C in the absence of radical-supplying polymerization initiators and regulators and an average molecular weight M of 400 to 4000 exhibit. 2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß die kontinuierliche Massepolymerisation des Monomerengemisches bei Verweilzeiten von < 30 Minuten durchgeführt wird.2. The method according to claim 1, characterized in that the continuous bulk polymerization of the monomer mixture is carried out with residence times of <30 minutes. 3. Druckfarbenbindemittel, hergestellt nach einem Verfahren gemäß Anspruch 1 oder 2, dadurch gekennzeichnet, daß das carboxylgruppenhaltige Copolymerisat einen Uneinheitlichkeitsfaktor bezüglich des Molekulargewichts U = Mw/Mn - 1 < 2 aufweist.3. Printing ink binder, produced by a process according to claim 1 or 2, characterized in that the copolymer containing carboxyl groups has a non-uniformity factor with respect to the molecular weight U = M w / M n - 1 <2. 4. Verwendung des carboxylgruppenhaltigen Copolymerisats gemäß einem der vorhergehenden Ansprüche als Bindemittel für wäßrige Druckfarben zum Bedrucken von Papier, Kunststoff- und Metallfolien.4. Use of the copolymer containing carboxyl groups according to one of the preceding claims as a binder for aqueous printing inks for printing on paper, plastic and metal foils.
EP83106412A 1982-07-10 1983-07-01 Use of binders based on carboxyl-containing copolymers in aqueous printing inks Expired - Lifetime EP0100444B2 (en)

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DE3225876 1982-07-10
DE19823225876 DE3225876A1 (en) 1982-07-10 1982-07-10 METHOD FOR PRODUCING PRINTING INK BINDERS AND THE USE THEREOF FOR AQUEOUS PRINTING INKS

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EP0100444A3 EP0100444A3 (en) 1984-06-06
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5296531A (en) * 1991-12-20 1994-03-22 Basf Aktiengesellschaft Pigment preparations
EP0858483A1 (en) * 1995-10-31 1998-08-19 Henkel Corporation Methods of preparing inorganic pigment dispersions
US6476170B1 (en) 1996-07-26 2002-11-05 Cook Composites & Polymers Co. Solid acrylic resin using a continuous tube reactor

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19542181A1 (en) 1995-11-13 1997-05-15 Hoechst Ag Solvent-free synthetic resins and synthetic resin mixtures
EP0913443A4 (en) * 1996-07-19 1999-10-06 Toagosei Co Ltd Heat-sensitive and pressure-sensitive adhesive sheet
US6232405B1 (en) * 2000-02-02 2001-05-15 Atofina Chemicals, Inc. SMA resin amic acids
US10927194B2 (en) 2016-07-20 2021-02-23 Basf Se Process for preparing an aqueous polymer dispersion having high chemical resistance

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1079603A (en) * 1965-01-08 1967-08-16 Basf Ag Print pastes
DE2345814A1 (en) * 1973-09-11 1975-03-20 Bp Benzin Und Petroleum Ag Copolymerising acrylic acid and styrene monomer - and short-stopping with solvent, giving coating, impregnating and rust-removing compsns.
DE2502172A1 (en) * 1975-01-21 1976-07-22 Basf Ag Anionic paper sizing agents - comprising water soluble salt of a copolymer of an olefin, (meth)acylic acid and maleic acid
DE2658857A1 (en) * 1976-12-24 1978-06-29 Hoechst Ag Copolymer resins useful as printing ink additives - prepd. by heating a cyclopentadiene cpd., an unsatd. aromatic cpd. and an unsatd. carboxylic acid cpd.
DE3026831A1 (en) * 1980-07-16 1982-02-18 Basf Ag, 6700 Ludwigshafen Continuous copolymerisation of monomer mixts. - contg. mono:vinyl aromatic cpd. and unsatd. carboxylic acid with heat and under periodic pressure fluctuation
EP0047889A2 (en) * 1980-09-11 1982-03-24 BASF Aktiengesellschaft Alcali-soluble resins based on copolymers of olefinically unsaturated carboxylic acids and olefines substituted by aromates, and their use as resin components in polymer dispersions

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3046476A1 (en) * 1980-12-10 1982-07-22 Basf Ag, 6700 Ludwigshafen BINDERS FOR COATING MATERIALS TO BE PROCESSED FROM THE MEL AND THEIR USE

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1079603A (en) * 1965-01-08 1967-08-16 Basf Ag Print pastes
DE2345814A1 (en) * 1973-09-11 1975-03-20 Bp Benzin Und Petroleum Ag Copolymerising acrylic acid and styrene monomer - and short-stopping with solvent, giving coating, impregnating and rust-removing compsns.
DE2502172A1 (en) * 1975-01-21 1976-07-22 Basf Ag Anionic paper sizing agents - comprising water soluble salt of a copolymer of an olefin, (meth)acylic acid and maleic acid
DE2658857A1 (en) * 1976-12-24 1978-06-29 Hoechst Ag Copolymer resins useful as printing ink additives - prepd. by heating a cyclopentadiene cpd., an unsatd. aromatic cpd. and an unsatd. carboxylic acid cpd.
DE3026831A1 (en) * 1980-07-16 1982-02-18 Basf Ag, 6700 Ludwigshafen Continuous copolymerisation of monomer mixts. - contg. mono:vinyl aromatic cpd. and unsatd. carboxylic acid with heat and under periodic pressure fluctuation
EP0047889A2 (en) * 1980-09-11 1982-03-24 BASF Aktiengesellschaft Alcali-soluble resins based on copolymers of olefinically unsaturated carboxylic acids and olefines substituted by aromates, and their use as resin components in polymer dispersions

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5296531A (en) * 1991-12-20 1994-03-22 Basf Aktiengesellschaft Pigment preparations
EP0858483A1 (en) * 1995-10-31 1998-08-19 Henkel Corporation Methods of preparing inorganic pigment dispersions
EP0858483A4 (en) * 1995-10-31 1998-10-07 Henkel Corp Methods of preparing inorganic pigment dispersions
US6197879B1 (en) 1995-10-31 2001-03-06 Henkel Corporation Methods of preparing inorganic pigment dispersions
US6476170B1 (en) 1996-07-26 2002-11-05 Cook Composites & Polymers Co. Solid acrylic resin using a continuous tube reactor

Also Published As

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EP0100444B1 (en) 1986-03-26
EP0100444A3 (en) 1984-06-06
DE3225876A1 (en) 1984-01-12
DE3362682D1 (en) 1986-04-30
EP0100444B2 (en) 1993-06-30

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